• International Journal of Technology (IJTech)
  • Vol 10, No 3 (2019)

One-step Synthesis to Enhance the Acidity of a Biocarbon-based Sulfonated Solid Acid Catalyst

One-step Synthesis to Enhance the Acidity of a Biocarbon-based Sulfonated Solid Acid Catalyst

Title: One-step Synthesis to Enhance the Acidity of a Biocarbon-based Sulfonated Solid Acid Catalyst
Yulia Nurul Ma’rifah, Iryanti Nata, Hesti Wijayanti, Agus Mirwan, Chairul Irawan, Meilana Dharma Putra, Kawakita Hidetaka

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Cite this article as:
Ma’rifah, Y.N., Nata, I., Wijayanti, H., Mirwan, A., Irawan, C., Putra, M.D., Hidetaka, K., 2019. One-step Synthesis to Enhance the Acidity of a Biocarbon-based Sulfonated Solid Acid Catalyst. International Journal of Technology. Volume 10(3), pp. 512-520

Yulia Nurul Ma’rifah Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Iryanti Nata Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Hesti Wijayanti Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Agus Mirwan Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Chairul Irawan Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Meilana Dharma Putra Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Kawakita Hidetaka Department of Chemistry and Applied Chemistry, Saga University, Saga 840-8502, Japan
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One-step Synthesis to Enhance the Acidity of a Biocarbon-based Sulfonated Solid Acid Catalyst

The main purpose of this study is to produce and generate a solid acid catalyst from biomass with high reactivity that can be used in catalytical reactions such as hydrolysis, and is environmentally friendly and reusable. A biocarbon-based sulfonated catalyst was prepared by the carbonization of palm empty fruit bunches (PEFB), followed by sulfonation. In order to enhance the acidity of the biocarbon, different concentrations of hydroxyethylsulfonic acid were added to the solution during sulfonation at 180o C for 4 h in a Teflon stainless steel autoclave. The H+ ion capacity of the biocarbon-sulfonated acid catalyst (BSC) was increased twofold (3.57 mmol/g) in the presence of 10% of hydroxyethylsulfonic acid and 10% of acrylic acid. X-Ray Fluorescence (XRF) analysis showed that the BC-SO3H contained 38% of S. The original structure of the PEFB after carbonization disintegrated from the fibrous materials onto porous carbon. The crystalline index (CrI) of the PEFB significantly decreased to about 32% and a wide broad peak of a X-Ray Diffraction (XRD) pattern of around 20-30o were observed, which shows that an amorphous biocarbon structure had been identified. Fourier Transform Infra-Red (FT-IR) analysis confirmed that the -SO3H, COOH and -OH functional groups were deposited on the carbon due to specific peaks at around 1180 cm-1, 1724 cm-1 and 3431 cm-1, respectively. Decomposition of the sulfonic groups on the biocarbon-sulfonated solid catalyst was observed from 227.9o C, as it shown by thermal gravimetric analysis (TGA). 

Acid catalyst; Biocarbon; Palm empty fruit bunch; Sulfonated; Sulfonation


Palm is one of the most important commodities in Indonesia due to its rapid development. The major product from the palm industry is Crude Palm Oil (CPO), but with its increasing production, the waste, that takes the form of empty fruit bunches, has increased. Nowadays, biomass and industrial waste have become very interesting issues as aspects of catalyst development, both in research and from the technical point of view, due to their valuable merit of industrial waste (Guerrero-Pérez et al., 2006; Kusrini et al., 2018). Biomass energy is an ideal clean and renewable energy source, characterized by its wide range of sources, low prices, strong reproducibility and less pollution creation (Wenjing et al., 2018).

In the using of solid acid catalysts, they are easy and efficient when separated from their products, are reusable and it is possible to apply them in wide of applications, but most such catalysts developed are expensive and quite difficult to prepare (Okuhara, 2002)Recently, work on sulfonated solid acid catalysts has attracted great attention from researchers for the hydrolysis reaction of cornstarch (Nata et al., 2015; Nata et al., 2017b) and biodiesel production from waste cooking oil (Zong et al., 2007; Nata et al., 2017a). Performance in the reaction of carbon-derived catalysts is dependent on the precursor as raw materials for carbon production and treatment processes (Tao et al., 2015). From the point of view of “green chemistry”, the sulfonated carbon catalyst has emerged as a promising solid acid catalyst (Jiang et al., 2012).

Theoretically, at low carbonization (400–600oC), biomass generates a highly cross-linked, multi-ringed, aromatic structure anchored to lignin that can be easily functionalized with catalytically active acidic groups by slow pyrolysis (Kastner et al., 2012). Generally, a two-step process is involved in the production of sulfonated carbonaceous materials. Saccharide is incompletely carbonized at a temperature of > 400°C for >15 h under an inert atmosphere. A large amount of sulphuric acid use in the sulfonation process at a high temperature for the inactive surface of carbonaceous material (Zong et al., 2007). This process uses hazardous material and a large amount of harmful waste is produced; moreover, the carbon in the concentrate sulphuric also needs special attention for its separation and treatment.

Hydrothermal carbonization (HTC) is a thermochemical process capable of converting wet biomass into a carbon-enriched solid as hydrochar. The HTC process consists of several reactions conducted both in series and in parallel, including hydrolysis, dehydration, decarboxylation, condensation and aromatization (Merzari et al., 2018). HTC is process which involves the decomposition of several carbohydrates in aqueous solution at 180°C. This method is cheap, mild and environmental friendly, as no organic solvents, catalysts or surfactants are used (Titirici et al., 2007). In a previous study, Xiao et al. (2010) performed hydrothermal treatment with hydroxyethylsulfonic acid as a sulfonate agent to produce carbon from glucose and used it for an esterification process in order to examine its catalytic ability. However, this procedure only achieved 1.7 mmol/g of acidity and still owned little of functional groups. Therefore, to generate carbonaceous material loaded with carboxylic groups, known as an active group that participates in the reaction, acrylic acid was added (Bautista-Toledo et al., 2005). In order to produce a high content of functional groups on the carbon material, it is possible to modify the surface by a one-step HTC process for sulfonation and thus improve the acidity of the carbon.

This work focuses on the effect of hydroxyethylsulfonic acid concentration and the addition of acrylic acid during the hydrothermal process. Therefore, the characterization of aspects such as acidity, morphological structure, crystalline structure, functional groups and thermal gravimetric analysis was investigated.


The strong acid content, rich of sulfonic and carboxylic groups of materials could be easily synthesized by a one-step hydrothermal process using biocarbon from incomplete carbonization of PEFB, and in the presence of hydroxyethylsulfonic, acrylic and citric acid in mild conditions. The simplicity of operation, high activity and stability, low cost of raw materials and reusability are the main features of this original biocarbon-based sulfonated solid acid catalyst, which demonstrates that biocarbon has great potential for green processes in various catalytic applications.


The authors are grateful for the financial support from International Research Collaboration and Scientific Publication (contract No. 040/UN8.2/PL/2018), Ministry of Research, Technology and Higher Education, Republic of Indonesia.  

Supplementary Material
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